A Textbook of Physical Chemistry by Arthur Adamson (Auth.)

By Arthur Adamson (Auth.)

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The reality of a critical point can be seen by means of the following type of experiment. A capillary tube is evacuated and then partly filled with liquid, the remaining space containing no foreign gases but only vapor of the substance in question; the tube is then sealed. On heating, opposing changes take place. The liquid phase increases its vapor pressure, and the vapor density increases as vapori­ zation occurs; this acts to diminish the volume of liquid phase. On the other hand, the liquid itself expands on heating.

1-8. However, while the broken line joining the end points of the condensation lines can be fairly well established, its exact maximum point is hard to fix exactly. This locus may alternatively be plotted as temperature versus the equilibrium vapor and liquid densities pv and px as illustrated in Fig. 1-15. A useful observation, known as the law of the rectilinear diameter, states that the average density / o av= (pi + />v)/2 is a linear function of temperature, as also illustrated in the figure.

0 g mole" ? 1-17 Let n° be the number of moles of N 0 introduced into a liter volume at 25°C. Partial 2 4 dissociation into N 0 occurs, and the equilibrium pressure is recorded. 8550 [Adopted from F. H. Verhoek and F. Daniels, / . Amer. Chem. Soc. ] Calculate each K [Eq. (1-22)] and the true K by extrapolation to zero pressure. 8 in the Hougen-Watson chart (Fig. 1-10) ends abruptly. c Reproduce this curve in a sketch, and show by means of a dotted line what a continuation of it should look like.

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